Proceedings of MATSUS Spring 2024 Conference (MATSUS24)
DOI: https://doi.org/10.29363/nanoge.matsus.2024.387
Publication date: 18th December 2023
Halide perovskites have been attracted as potential candidates in various electronic devices such as memristors and neuromorphic devices with superior resistive switching properties such as low power consumption, scalability, and compositional and mechanical flexibility as well as photovoltaics, LED, and so on. Among them, we report here low-dimensional lead-free halide perovskites for the resistive switching memory devices and propose their potential applicability in multi-functional electronic devices using the resistive switching characteristics. Although most studies have been focused on the lead-based halide perovskites, it is necessary to focus the research on lead-free halide perovskites without toxicity of lead for various viable electronic applications such as tin, copper, antimony, or bismuth-based materials. Here we found that copper (Cu2+)- and bismuth (Bi3+)-based halide perovskites can be suitable candidates for a variety of applications, especially memristor devices due to their visible characteristic electrical traits and improved stability. With these reports, we also suggest materials and devices design perspectives for multi-functional electronic devices including next generation memristors. For copper(II)-based halide perovskites, 2-dimensional (2D) (BzA)2CuBr4 (BzA = benzylammonium) perovskite was synthesized on Pt substrate, which retained a higher ON/OFF ratio over 108 even at lower operational voltage around +0.2 - -0.3 V. Longer endurance over 2,000 cycles was observed with Schottky conduction at HRS. [1] For bismuth (III)-based halide perovskites, layered double perovskite with chemical formula of BA2CsAgBiBr7 was synthesized on Pt substrate by phase conversion of 3D Cs2AgBiBr6, which showed endurance of 1,000 cycles and retention time over 2×104 s at operational voltage as low as 0.5 V, along with ON/OFF ratio as high as ~107. [2] Both the previously reported 3D counterparts on ITO substrate [3] and 2D Ag-Bi system [2] here showed excellent memristor properties, but especially the ON/OFF ratio of 2D Ag-Bi system was five orders of magnitude larger than those of 3D counterparts. Modification of Schottky conduction at high resistance state (HRS) is found to be responsible for high ON/OFF ratio in low-dimensional structure. In addition, as another study of bismuth-based materials, we fabricated a low-dimensional Cs3Bi2Br9-based memristor with a thin film less than 1 micrometer, where synthetic Cs3Bi2Br9 powder precursor enabled uniform thin film formation.[4] Thin film also exhibited low operating voltages as +0.44 V with gradual current increase at the SET process with reliable cell-to-cell and device-to-device resistive switching behavior. It was also found that the 2D low-dimensional copper and bismuth-based halide perovskites studied here showed much better stability under high humidity and at elevated temperature than the 3D and/or lead-based counterparts, which is beneficial for practical applications. Therefore, it was confirmed that low-dimensional lead-free halide perovskite materials are promising candidates for resistive switching memory devices, and we also expect that various halide perovskites can be derived and applied to multi-functional electronic devices including memristors, neuronic or synaptic devices, and so on.
This work is funded by the European Research Council (ERC) via Advanced Grant 101097688 (PeroSpiker).